JP2006192127A - Deodorizing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve the problem that there has been no simple method to get rid of chronic odor, which usually arises as time goes on despite of daily cleaning or deodorizer using in a water section space. <P>SOLUTION: This method continuously prevents odor from being generated a narrow gap or the like of a toilet, bathroom, kitchen, lavatory or the like, which cannot be washed by water usually and got at when cleaned in the water section space, from evolving odor by spreading liquid detergent containing components to inhibit activity of enzymes for facilitating odorant generation through spraying or the like. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a method for suppressing the generation of odor.

In recent years, as consumers are increasingly interested in the living environment, means and techniques for removing unpleasant odors around them have been demanded as a familiar issue. In particular, odors containing nitrogen atoms such as amines and ammonia are bad odors that give unpleasant sensations to everyone because of their natural odor or strong irritation to the nasal cavity.
Examples of methods for preventing the generation of these unpleasant odors include the following.

Patent Document 1 discloses that urine adheres to the urinal by preventing generation of ammonia and the accompanying increase in pH in the urinal by flowing wash water containing a component that inhibits urease, which is a urea hydrolase, in flushing the urinal. A method of suppressing this is described.
In Patent Document 2, a liquid agent containing 0.5 wt% to 20 wt% of copper gluconate as an active ingredient is sprayed on garbage, and the odor component and the active ingredient containing nitrogen and sulfur generated from the garbage are chemically treated. A method for deodorizing by reaction and a deodorizing method by an antibacterial action of an active ingredient are disclosed.
In Patent Literature 3, a liquid agent containing 1.0 wt% to 20 wt% of a zinc compound and 0.1 wt% to 5.0 wt% of a nonionic surfactant having an HLB of 4 to 20 as an active ingredient is used as an industrial waste. A deodorizing method is disclosed in which odor is removed by spraying or adding to animal organic residues and waste water exuded therefrom.
In Patent Document 4, a liquid agent containing an active ingredient that exhibits a deodorizing action by chemical reaction or neutralization reaction or masking with odor and a water-soluble polymer having an average molecular weight of 2000 to 20000 is applied to a fiber such as clothing. There has been disclosed a deodorizing method that can effectively exert the deodorizing action of the active ingredient by spraying and preventing the active ingredient from falling off the fiber by the action of the water-soluble polymer.
In Patent Document 5, a liquid agent containing an active ingredient that develops a deodorizing action by chemical reaction or neutralization reaction or masking with odor is sprayed into a space where an unpleasant odor caused by smoking drifts to make it non-bromide. A deodorizing method is disclosed.

WO96 / 6237 Japanese Unexamined Patent Publication No. 8-198709 JP 2001-321427 A JP 2001-37861 A JP 2001-95906 A

Deodorizing / deodorizing method by spraying liquid into the odor generating source or the space where odor occurs such as odor generating method such as washing water containing active ingredients directly to toilet as mentioned above Has traditionally existed. However, even if cleaning is performed in a water environment or using the above deodorizing and deodorizing methods, dirt remains in areas such as gaps that cannot be accessed by daily water cleaning or wiping cleaning. Odor is generated based on the remaining dirt with the passage of time. Accordingly, an object of the present invention is to provide a method for suppressing the generation of odors that are chronically present in the water space.

In the present invention, in order to solve the above-mentioned problems, a liquid agent containing a component that inhibits the activity of an enzyme that promotes the generation of an odorous substance to a site that cannot normally be washed in a water space and that cannot be reached during cleaning is provided. By applying this method, a method for continuously preventing the generation of odorous substances is provided.

ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to prevent the odor which drifts chronically in the water circumference space.

  Hereinafter, specific embodiments of the present invention will be described.

In the present invention, the “space around water” is a space where water is used in daily life, and specifically refers to a toilet, a bathroom, a kitchen, a washroom, and the like. In these water spaces, cleaning such as water washing or wiping is routinely performed.

In the present invention, "parts that can not usually be washed with water and not reachable during cleaning" means that the above-described washing with water is not possible, and cleaning such as wiping is not sufficiently performed because hands cannot be entered in daily cleaning, It is the part where dirt remains. Specifically, in the toilet space, a gap generated in a portion where the Western-style toilet bowl and the floor are in contact, a gap generated in a portion where the Western-style toilet is in contact with the wall, a gap generated in the toilet seat and the toilet seat mounting surface, a toilet lid In the gap between the toilet seat and the toilet seat, the gap between the local cleaning device and the toilet seat mounting surface, the gap between the toilet seat and the tank, Examples include gaps that occur, gaps that occur in the part where the urinal and the wall contact, gaps that occur in the part where the urinal and the floor contact, and gaps that occur in the operating part such as a portable toilet lid and toilet seat mounting part. In the unit type bathroom space, the back of the apron part of the bathtub or the joint of the panel material constituting the wall can be mentioned. In the kitchen, there are various places in the grilled fish, around the drain outlet, around the drain pipe, and the gap between the system kitchen and the wall. In the washroom, there is a gap between the washstand and the wall.

In the present invention, the term “generation of odorous substance” means that the odor-causing substance that does not feel so unpleasant with its own odor is variously caused by the catalytic action of the enzyme, such as hydrolysis reaction, oxidation reaction, reduction reaction, etc. It is said to cause the reaction of and change to odorous substances. The causative substances of odor generation include lipids and proteins contained in foods that cause nitrogenous and sulfurous odors, urea contained in excrement urine and sweat, uric acid, etc. This is not a limitation.

The “enzyme” in the present invention serves as a catalyst for the above various reactions, and includes enzymes contained in animal excreta as well as enzymes possessed or secreted by microorganisms. Examples include urease, which is a hydrolase that generates ammonia odor using urea as a substrate, and uricase, which is an oxidoreductase that generates allantoin odor using uric acid as a substrate. In addition, the said microorganisms are not specifically limited, It is bacteria, yeast, mold | fungi generally existing in an everyday environment, and colon_bacillus | E._coli, Staphylococcus aureus, Pseudomonas aeruginosa, Bacillus natto, etc. are mentioned.

In the present invention, “inhibiting the activity of the enzyme” means that the odor-causing substance acts directly on the enzyme and loses its activity as a catalyst so as not to cause a reaction in which the odor-causing substance becomes an odor substance. In other words, unlike so-called antibacterial, which acts on bacteria and sterilizes, it is not necessary to kill bacteria and microorganisms themselves, and aims to inhibit activities related to the generation of odorous substances of microorganisms.

In the present invention, `` applying a liquid agent '' means spraying using a propellant, nozzle with trigger, spraying / dispersing with a pump, application using a brush / sponge / cloth, etc. by any existing method, It means that a liquid agent is brought into contact with the site and penetrated by a physical action such as capillary force, surface tension, or gravity. The purpose of the present invention is to allow the liquid agent to reach the part sufficiently, and it is desirable that the part is sufficiently close to the part in means such as spraying and spraying. The applied site may get wet.

In the present invention, “preventing the generation of odorous substances” means that the activity of an enzyme that promotes the generation of odorous substances by applying a liquid agent by spraying or the like to a site where the cleaning is not complete and dirt remains. By suppressing the unpleasant odor, the unpleasant odor generated by using the residual soil as a causative substance is cut off from the source, and the generation of the unpleasant odor is continuously prevented for at least one week. In other words, unlike conventional methods of deodorizing by reacting with odorous substances known as deodorizing methods and methods of masking odors with fragrances, liquids are applied to residual dirt that cannot be removed by daily cleaning. By doing this, it means preventing the chronic odor drifting around the water. In the present invention, a liquid agent is applied in advance to a site where the hand is not used during cleaning, and odor generated by subsequent use can be prevented. In addition, even when an odor already exists, a method of obtaining a deodorizing effect by applying a liquid agent to the site can also be adopted. However, the method of applying the liquid agent in advance as in the former is more preferable from the viewpoint of removing chronic odors.

The “compound containing nitrogen” refers to a compound having a nitrogen atom in its molecular structure, such as ammonia and various amines.

In the present invention, the “divalent metal ion” is a metal ion having a positive divalent ion valence. As a result of examining various metal ions, it was found that divalent metal ions having a smaller ionization tendency than aluminum are effective in suppressing enzyme activity, and copper ions, zinc ions and nickel ions are preferable. Of these, copper ions were the most effective. It should be noted that silver ions and trivalent iron ions, which are known to be effective in deodorization and deodorization by reaction with antibacterial or odorous substances, could not suppress enzyme activity or the effect of suppression was small. Even with divalent metal ions, enzyme activity could not be suppressed with metal ions having a large ionization tendency such as calcium ions and magnesium ions.

Inhibition of enzyme activity is considered to be achieved by coordination of the metal ion to the enzyme protein. Proteins that form enzymes have peptide bonds, disulfide bridges, and amino acid residues such as amine groups, carboxyl groups, and thiol groups. Considering that the effect of silver ions is small, divalent metal ions such as copper ions, zinc ions, and nickel ions are strongly coordinated to amino acid residues such as peptide bonds, amine groups, and carboxyl groups. Therefore, it is considered that the activity of the enzyme active center as a catalyst is effectively suppressed. Among them, the copper ion has the best performance for inhibiting the activity of the enzyme.
Copper ions easily form chelate compounds by coordination of carboxyl groups contained in materials such as ethylenediaminetetraacetic acid, compared to other metal ions including zinc ions and nickel ions. There is a feature that a chelate compound is easily formed by coordination of an amine group contained in. Because of these properties, it is considered that copper ions easily coordinated to the enzyme structure and inhibited the enzyme most effectively. The chelate compound is a compound having a structure in which two or more “coordinating atoms” of one “molecule or ion” are coordinated so as to sandwich a metal ion. Here, the “molecule or ion” refers to the ethylenediamine and ethylenediaminetetraacetic acid. The “coordinating atom” refers to nitrogen atoms of two amine groups in the structure in an ethylenediamine molecule, and negatively charged oxygen atoms of four carboxyl groups in the structure in ethylenediaminetetraacetic acid. Point to that.

In the present invention, a salt is a product in which a divalent metal ion is bonded to form a water-soluble electrolyte, and any salt can be used. However, a salt using an organic acid as a counter ion is generally safe. Since it is excellent, what is added as an organic acid salt is preferable. Examples of organic acids include saturated aliphatic monocarboxylic acids such as formic acid and acetic acid, saturated aliphatic dicarboxylic acids such as malonic acid, succinic acid and adipic acid, non-reactive substances such as oleic acid, fumaric acid and maleic acid. It can be arbitrarily selected from those containing a carboxyl group such as saturated aliphatic carboxylic acid, carbocyclic carboxylic acid such as benzoic acid, citric acid, malic acid, gluconic acid and the like. Among them, copper gluconate and zinc gluconate are designated as standard-standard food additives that can be used for nutritional functional foods, and are safe for daily use.

An object of the present invention is to inhibit an enzyme that promotes the generation of odorous substances, and the metal ions in the solution exhibit a sufficient effect at a low concentration of 0.001 mM to 1.00 mM. That is, it acts at a concentration lower than the concentration at the time of deodorizing by reacting with the generated odor substance or the concentration at which the antibacterial effect is expressed. Therefore, even if it is a colored liquid such as a solution containing copper ions, which is most effective, the concentration is low, so it can be used in large quantities in the same part or even if it is used over a long period of time. There is no problem such as coloring of the application part. In addition, the low concentration ensures sufficient safety.

In the present invention, the solvent constituting the liquid agent is mainly water, but in view of the use and peripheral members of the application site, a solvent having higher volatility than water such as ethanol and propanol may be added and used. .

In the liquid preparation according to the present invention, an ingredient arbitrarily selected for increasing the added value can be added as long as the function of the essential component for suppressing the enzyme activity can be sufficiently exerted and the safety of the liquid preparation can be secured. Deodorant that does not bromide by reacting with any odorous component, porous adsorbent deodorant such as activated carbon, zeolite, or apatite that adsorbs odor and does not bromide, eliminates odors such as platinum, palladium, titanium oxide, etc. Examples include odorous catalysts, antibacterial / antifungal agents that suppress the growth of microorganisms, additives such as dispersants, emulsifiers, thickeners, gelling agents, preservatives, pH adjusters, and various fragrance ingredients.

In evaluating the deodorizing performance of the odorous substance by the liquid agent according to the present invention, the concentration of the generated odor is evaluated using a gas tech detector tube. In the evaluation 2 shown later, amines can be generated in addition to ammonia. However, since both gases interfere with each other in the detection tube and the respective concentrations cannot be detected, evaluation is performed with a detection tube for ammonia measurement. The concentration indicated by the detector tube was taken as the unpleasant odor concentration. In addition, in the case of the odor substance concentration below the measurement limit of the detector tube, “ND” was written in the result.

Table 1 summarizes the formulation examples evaluated in the present invention.

Evaluation 1: Enzyme activity inhibition performance test 1 of solution
In a 5 liter Tedlar bag, 15 g of 1.73 wt% urea water and 0.7 g of the solutions of Formulation Examples 1 to 19 listed in Table 1, 3750 ppm urease (manufactured by Wako Pure Chemical Industries, Ltd., derived from Nata beans, 80 to 150 units) / Mg) 0.1 g of an aqueous solution was mixed, and the concentration of ammonia generated in the bag was measured over time.
The determination of the liquid agent in which the amount of ammonia generated after the reaction for 3 hours was less than 3 ppm was “OK”, and “NG” in other cases.

The test results of Evaluation 1 are summarized in Table 2.

In Table 2, as shown in the evaluation results of the liquid preparations of Formulation Example 1 to Formulation Example 5, Formulation Example 7, Formulation Example 10, Formulation Example 11, and Formulation Example 19, divalent metal ions having a concentration of 0.001 mM or more, It was found that copper ions, zinc ions, and nickel ions can effectively inhibit enzyme activity at low concentrations. Only the deodorant that deodorizes by neutralization reaction with the ammonia of Formulation Example 14 and Formulation Example 15 or only the deodorant that deodorizes by chemical reaction with the ammonia of Formulation Example 16 cannot inhibit the enzyme activity, Although the deodorizing performance exceeding the above standard cannot be obtained, as shown in Formulation Example 6, Formulation Example 8 and Formulation Example 9, these components can be used by mixing with the metal ions.

Evaluation 2: Enzyme activity inhibition performance test 2 of solution
In a 5 L Tedlar bag, 15 g of actual urine and Formulation Example 1, Formulation Example 6, Formulation Example 8, Formulation Example 9, Formulation Example 11, Formulation Example 12, Formulation Example 14, Formulation Example 16, Formulation Example 17 in Table 1 In addition, 1 g of the liquid agent described in Formulation Example 18 and 2 g of the dirt liquid collected from the gap between the toilet bowl and the toilet seat were mixed, and the concentration of unpleasant odor containing ammonia and amine generated in the bag was measured over time. The amount of urease contained in the soil solution collected from the site was 32 μg / ml in terms of a urease-derived urease reagent (100 units / mg).
The determination of the liquid agent in which the odor intensity of ammonia / amines during the reaction for 10 days was less than 20 ppm was “OK”, and “NG” in other cases.

The test results of evaluation 2 are summarized in Table 3.

From Table 3, in the liquid compositions of Formulation Example 1, Formulation Example 6, Formulation Example 8, and Formulation Example 9, the enzyme acts on the soil remaining in the toilet bowl that generates an unpleasant odor in the presence of actual urine. It also showed an inhibitory effect and demonstrated excellent deodorizing performance.

Evaluation 3: Evaluation of deodorization performance according to the application site and application method of liquid agent The evaluation of deodorization performance of the liquid agent according to the difference in application site and application method was carried out by 20 monitors who answered that there was a clearly unpleasant odor in the toilet space. . The liquid agent was filled in Mitani Valve Co., Ltd. trigger type spray pump Z-305 series. The liquid agent used, application site, and application method were as follows.
A table in which the liquid preparation of Formulation Example 8 in Table 1 was sprayed once each from a distance of 10 cm with respect to a gap generated between the toilet seat and the toilet seat mounting surface and a gap generated between the western toilet bowl and the floor surface. To the front toilet space from the position of the height of 150 cm of the toilet entrance, the solution of Formulation Example 8 of Table 1 sprayed three times from the distance of 50 cm with the liquid of Formulation 1 of 1 toward the water storage part in the Western-style toilet In the same manner as in 1), the liquid agent of Formulation Example 16 in Table 1 sprayed five times toward the gap is formed between the toilet seat and the toilet seat mounting surface, and the gap generated at the portion where the western toilet bowl and floor are in contact with each other. As the deodorizing performance sprayed once from a distance of 10 cm, the change in odor intensity in the space after spraying was evaluated over one week. The target odor used for determination was set as follows.
Target odor: The odor intensity of the target odor used for judgment of unpleasant odor, stuffy odor, urine odor, raw odor, and scent that is not well understood was set as follows.
Odor intensity 5: Odor odor intensity clearly understood 4: Odor odor intensity clearly understood by sniffing 3: Odor odor intensity clearly understood 2: Odor intensity almost odorless 1: Target odor at the start of the test before applying a liquid solution that does not smell at all The determination when the odor intensity of the target odor after one week has been reduced by 2 points or more is “OK”, and “NG” otherwise.

FIG. 1 shows the odor intensity evaluation results for one week when the method 1) is used. As shown in this result, it can be seen that an excellent deodorizing effect can be obtained by applying a liquid agent containing low-concentration copper gluconate to a part that cannot be usually washed with water and is not accessible at the time of cleaning.
FIG. 2 shows an odor intensity evaluation result for one week when the method 2) is used. FIG. 3 shows a change in odor intensity for one week when the method 3) is used. Even if it was not usually washed with water and sprayed with a liquid other than the parts that could not be reached during cleaning, the deodorizing effect could not be obtained.
FIG. 4 shows the odor intensity evaluation results for one week when the method 4) is used. It can be seen that a liquid agent that does not contain copper ions as an active ingredient cannot provide a sufficient deodorizing effect.

Evaluation 4: Evaluation of colorability by application of liquid agent White cotton cloth was dipped in the liquid agents described in Formulation Example 2, Formulation Example 8 and Formulation Example 20 described in Table 1, pulled up, and then air-dried as it was. Compared with a cotton cloth that had been subjected to the same operation with water, the one having almost no change in color tone was judged as “OK”, and the one in which discoloration was confirmed was judged as “NG”.

The test results of Evaluation 4 are summarized in Table 4.

As shown in Table 4, when the copper concentration exceeded 1 mM and reached 10 mM, the blue color of the solution itself became strong, and the cloth contacted with the solution was colored blue.

The deodorizing method of the present invention can be used to prevent the generation of odors in toilets, bathrooms, kitchens, toilets, and the like.

Figure showing the change in odor intensity for one week after spraying a liquid containing an active ingredient on a site where odor-causing substances are present and cannot be washed normally The figure which shows the odor intensity | strength change for one week after spraying the liquid agent containing an active ingredient to the water storage part in a western style toilet bowl. The figure which shows the odor intensity change for one week after spraying the liquid agent containing an active ingredient in the space where odor drifts Figure showing the change in odor intensity for one week after spraying a solution that does not contain an active ingredient onto a site where odor-causing substances exist and cannot be washed with water

Claims (4)

Occurrence of odorous substances is continually prevented by applying a solution containing ingredients that inhibit the activity of enzymes that promote the production of odorous substances to areas that cannot normally be washed with water in the surroundings of water and that cannot be reached during cleaning. how to The method of claim 1, wherein the odorous substance is a nitrogen-containing compound. The component that inhibits the activity of an enzyme that promotes the production of an odorous substance in the liquid preparation is a divalent metal ion, and contains at least one of copper ion, zinc ion, and nickel ion. Or a method according to claim 2 The method according to claim 3, wherein the metal ion is added as a water-soluble salt, and the concentration of the salt is 0.001 mM to 1.00 mM.

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